Stabilized photographic silver halede



Unite States Patent STABILIZED PHOTOGRAPHIC SILVER HALIDE EMULSIONSCONTAINING S-THIOCTIC ACID Charles Francis Hitchcock Allen, Bernard D.Illingsworth,

and John J. Sagura, Rochester, N .Y., assignors to Eastman KodakCompany, Rochester, N.Y., a corporation of New Jersey No Drawing. FiledJuly 11, 1957, Ser. No. 671,129

13 Claims. (21. 96-109) This invention relates to a fog-inhibiting agentor stabilizer for photographic silver halide emulsions, and a method ofpreventing scum in photographic silver halide emulsions containingcertain types of sensitizers.

It is well known that photographic emulsions on storage tend to losesensitivity and to become spontaneously developable without exposure tolight. There is normally a detectable amount of the silver salt reducedduring development in the areas where no exposure was given;

this is commonly called fog, and sometimes called N chemical fog whereit is necessary to distinguish between it and the effects of accidentalexposure to radiation; in this invention, we are not concerned with thelatter.

Fog depends both on the emulsion and the conditions of development; fora given emulsion it increases with the degree of development. Withconstant development conditions, it tends to increase with. time,temperature and relative humidity of storage conditions; it is commonpractice to make accelerated tests of the stability of photographicemulsions by storage at increased temperature or humidity, or both. Itis, of course, desirable to have V.

emulsions as stable as possible under the conditions of high temperatureand humidity which may occur in tropii cal climates, for example. Fogusually appears over the whole area of the sensitive coating, but whensevere, it frequently is non-uniform. Fog may also be caused by exposureto chemicals, for example, hydrogen sulfide and other reactive sulfurcompounds, hydrogen peroxide vapor, and strongly reducing materials.While antifoggants and stabilizers may protect, to some extent, againstsuch effects, it is normally understood that an antifoggant protectsagainst spontaneous growth of fog during prolonged storage or storage attemperatures and humidities, or during development to maximum contrastand speed, or both.

When high-speed negative emulsions containing an alkylene oxide polymeras a sensitizer are developed in high-solvent developers, such as. KodakDeveloper DK- 20, a brown image tone or a brown surface deposit commonlycalled scum is observed.

It is, therefore, an object of our invention to provide a method ofstabilizing photographic silver halide emulsions. A further object is tomaintain the sensitivity and fog of silver halide emulsions at or closeto initial optimum values under keeping conditions of high temperatureand humidity. Another object is to provide a means of reducing orremoving scum which forms during development of high-speed negativeemulsions containing alkylene oxide polymers as emulsion sensitizers.Still another object is to provide photographic silver halide emulsionscontaining a stabilizer or fog-inhibiting agent. Other objects willbecome apparent from a consideration of the following description andexamples.

According to our invention, photographic silver halide emulsions can bestabilized against the formation of spontaneous fog by incorporating inthe emulsions 5- thioctic acid. This compound can be illustrated by thefollowing formula:

7 H2O S CHzCHzCHiCOOH C H H:

for this particular purpose, can be added either to the empil sion, to apre-bath or to the developing solution itse For the purpose ofinhibiting fog formation, the 5- thioctic acid can be added to theemulsion during the process of manufacture to avoid loss of sensitivityand to inhibit the growth of fog with passage of time under non-idealconditions of storage.

A solution of the S-thioctic acid of the invention when added insuitable concentration, before coating, to unsensitized, chemicallysensitized, or optically sensitized photographic emulsions does notappreciably alfect the sensitometric values for sensitivity and fog whenmeasurements are made soon after coating. When sensitometricmeasurements are made at appreciable intervals of time, at elevatedtemperatures and dry or somewhat humid conditions, this compound doesstabilize photographic speed and maintain fog at a low level.

The preparation of silver halide emulsions involves three separateoperations: (1) the emulsification and digestion or ripening of thesilverihalide, (2) the freeing of the emulsion from excess solublesalts, usually by washing, and (3) the second digestion orafter-ripening to obtain increased sensitivity. '(Mees, The Theory ofthe Photographic Process (1942).). We prefer to add the fog-inhibitingagents after the final digestion or afterripening, although they canadvantageously be added prior to digestion. I I

The photographic emulsions used in practicing our invention aregenerally of the developing-out type; also, it is to be understood thatphotographic emulsions of varying halide content can advantageously beused. The 5-thioctic acid used in our invention has been foundparticularly useful when employed in conjunction withgelatino-silver-bromiodide emulsions, although it can also beadvantageously employed in other silver halide emulsions, such asgelatinosilver-chloride, bromide, chlorobromide, chlorobromiodide, etc.

The emulsions can also be chemically sensitized by any of the acceptedprocedures. The emulsions can be digested with naturally active gelatin,or sulfur compounds can be added such as those described in Sheppard US.Patent 1,574,944 and U.S. 1,623,499, and Sheppard and Brigham US. Patent2,410,689.

The emulsions can also be treated with salts of the noble metals such asruthenium, rhodium, palladium, iridium and platinum, all of which belongto group VIII of the periodic table of elements and have an atomicweight greater than 100. Representative compounds are ammoniumchloro-palladate, potassium chloroplatinate and sodium chloropalladite,which are used for sensitizing in amounts below that which produces anysubstantial fog inhibition, as described in Smith and Trivelli US.Patent 2,448,060, and as antifoggants in higher amounts, as described inTrivelli and Smith US. Patents. 2,566,245 and 2,566,263. I

The emulsions can also be chemically sensitized with gold salts asdescribed in Waller and Dodd US. Patent 2,399,083, or stabilized withgold salts as described in Patented Aug.-9, 1960 3 Damschroder U.S.Patent 2,597,856 and Yutzy and Leermakers U.S. Patent 2,597,915.Suitable compounds are (potassium chloroaurite, potassiumaurithiocyanate, potassium chloroaurate, auric trichloride and2-aurosulfobenzothiazole methochloride.

The emulsions can also be chemically sensitized with reducing agentssuch as stannous salts (Carroll U.S. Patent 2,487,850), polyamines suchas diethylene triamine (Lowe and Jones U.S. Patent 2,518,698),polyarnines, such as spermine (Lowe and Allen U.S. Patent 2,521,925), orbis-(,B-aminoethyl) sulfide and its watersoluble salts (Lowe and JonesU.S. Patent 2,521,926).

The emulsions can also be stabilized with the mercury compounds ofAllen, Byers and Murray U.S. Patent 2,728,663, Carroll and Murray U.S.Patent 2,728,664, and Leubner and Murray.U.S. Patent 2,728,665.

The S-thioctic acid is effective in the presence or absence of opticalsensitizing dyes. Since optical sensitizing may affect stability ofemulsions with respect to sensitivity, fog and latent image changes, theaction of the S-thioctic acid of this invention is not completelyindependent of optical sensitizing or other emulsion variables. We havefound, however, that both unsensitized emulsions and emulsionssensitized with cyanine and developed for 18 minutes at 68 F. in adeveloper (D-l9) having the following composition:

Water, about 125 F. (50 C.) cc 500 Kodak Elon developing agent gram 2.0Kodak sodium sulfite, desiccated do 90.0 Kodak hydroquinone do 8.0 Kodaksodium carbonate, monohydrated -do 52.5 Kodak potassium bromide do 5.0

Cold water to make 1.0 liter.

Fresh tests and incubation tests (1 week at 120 F., constant humidity)were also run for the same emulsion batches with development for 5minutes in a normal developer (DK-SO) (same as used in Table Ia below)for comparison with forced development (D-l9). The speed, gamma and fogfor each of the emulsion coatings were measured. The speed figure shownin the following table is on a logarithmic scale, obtained by theformula l00(1l0g E), where E is the exposure in metercandle-seconds ofsunlight quantity required to produce a density of 0.30 above fog.Consequently, a difference of about speed units represents a differenceof about 100 percent in emulsion speed. The results are given in thefollowing table:

Table I 5 min. Kodak Developer DK50 18 min. Kodak Developer D-19 CoatingNumber Addenda Fresh 1 Wk. 120 Inc. res

CR 7 Fog C/R 'y Fog C/R 7 F08 Speed Speed Speed 311 1. 25 15 205 1. 25.37 332 1. 07 .33 (b) 5-Th10ct 1c 2 1d (I) 3.0 gJmole g 313 1, 34 12 2910, 3s .11 333 1.10 .18 (c) D -6-th1oct1c ae1d I) 0.03 21 6 AgX 311 1. 2414 300 1. 2s .15 332 1. 25 .20 DL-6-th10ct1c ac d (II) 0.3 gJmole AgX301 1,15 10 292 1. 07 .13 330 1. 32 .23 (e DL6-th1oct1c and (II) -0g-/m01e AgX 297 11 237 1. 13 13 321 1. 50 .1?- PEG 1500 of oleyl alcohol0- -l e g 335 1.0a 13 321 0. s0 .41 354 1.05 .41 0 -lmole plus (I) 3 s-ls 32s 1. 04 15 315 0. s0 .22 315 1.12 .25 -l ole I) 0.03 27 A 325 1.0513 320 1. 05 .21 341 1. 11 .36 (I 0- g-/mo1e I) 0.3 al ol 12 316 1.00 14305 1. 04 .15 340 1.12 .25 -lmoie (I 3.0 e/ AgX 304 0. 95 11 286 1. 10.21 325 1. 31 15 or merocyanine dyes, or both, can be treated with 5-thioctic acid according to our invention.

The S-thioctic acid useful in practicing our invention can be preparedas described in Jour. Am. Chem. Soc., vol. 76 (1954), page 1828.

It has been previously proposed to sensitize photographic silver halideemulsions with 6-thioctic acid. See U.S. Patent 2,728,668, issuedDecember 27, 1955. This acid can be represented by the followingformula:

However, 6-thioctic acid does not have the desirable stabilizingproperties of 5-thioctic acid, particularly when emulsions containingthe same are subjected to forced development. A comparison of theproperties of the two acids in this respect is given in Table I below.These data were obtained using an ordinary high speed bromiodideemulsion chemically sensitized with sulfur and gold compounds, andspectrally sensitized with a cyanine dye. A separate series of tests wasrun for an identical batch of emulsion which had been chemicallysensitized with the oleyl ether of polyethylene glycol (PEG) (molecularweight about 1500) (0.75 g./mol. AgX). This particular chemicalsensitizer provides useful speed increases, but also produces anincrease in fog. Each series of emulsions which had been coated on acellulose acetate support were exposed on a Kodak Ib sensitomer The sametype of emulsion used in arriving at the data in Table I above wastreated with S-thioctic acid in the amounts shown in the followingtable, and the treated emulsions compared with a similar batchcontaining no S-thioctic acid, both where the emulsions contained nochemical sensitizer (the same oleylether of polyethylene glycol used inTable l) and where the emulsions contained this sensitizer in the sameamounts used in Table I. A portion of each emulsion was coated on acellulose acetate support and incubated for one week at a temperature ofF. and constant relative humidity (obtained by placing the coatings inclosed containers, the ambient temperature being about 70 F. andrelative humidity about 55% prior to sealing the containers).

The efficiency of the S-thioctic acid was determined by measuring thespeed, gamma and fog of the incubated emulsions containing 5-thiocticacid and comparing these measurements with those of the same batch ofemulsion before incubation. Similar measurements were made with aphotographic emulsion containing no S-thioctic acid both before'andafter incubation. The coatings were then exposed on an intensity scalesensitometer (Eastman Type Ib) and developed for 5 minutes in adeveloper having the following composition:

Grams N-methyl-p-aminophenol sulfate 2.5 Hydroquinone 2.5 Sodium sulfite(desiccated) 30.0 Sodium metaborate 10.0 Potassium bromide 0.5

Water to make 1 liter.

alkylene oxides with aliphatic acids, e.g., lauric acid and glycine,condensation products of alkylene oxides with aliphatic amines oramides, e.g., glycine and lauryl amide, and condensation products ofalkylene oxides with phe nols, e.g., phenol. The preparation of thesecondensation products is described in U.S. Patent 1,970,578,Condensation products of alkylene oxides with hexitol ring Table Ia5-Thioctic Oleyl Fresh Tests Incubation, 1 Week at cid, Ether, 120 F.Coating g./mol g./mol.

AgX AgX Speed Gamma Fog Speed Gamma Fog none none 305 1. 24 16 292 1. 343. 0 none 307 1. 21 12 296 1.01 11 none 0. 75 328 l. 02 18 306 81 48 3.0. 75 323 97 14 310 83 21 The S-thioctic acid useful in practicing ourinvention dehydration products as described in U.S. Patent can be usedin various kinds of photographic emulsions. In addition to being usefulin ordinary non-sensitized emulsions, it can also be used inorthochromatic, panchromatic and X-ray emulsions. If used withsensitizing dyes, it can be added to the emulsion before or after thedyes are added. Suitable dispersing agents for the silver halideemulsions stabilized according to our invention comprise gelatin, orother colloids, such as collodion, albumen, cellulose organicderivatives, synthetic resins, etc.

The optimum amount of S-thioctic acid as a fog-inhibiting agent can bedetermined by making the customary tests employed in emulsion making. Ofcourse, the optimum amount for a given emulsion will vary depending onthe presence of emulsion addenda, such as chemical sensitizers, opticalsensitizers, etc. In general, we have found that from 0.25 to 4.0 g. ofS-thioctic acid'per mole of silver halide is sufficient for the purposesof our invention.

As indicated above, the S-thioctic acid of our invention is particularlyuseful in inhibiting or preventing the formation of scum during thedevelopment of high-speed negative emulsions which have been sensitizedwith an alkylene oxide polymer.

The alkylene oxide polymers used .to sensitize the emulsions may be ofvarious types. from which the polymers are derived contain from 2 to 4carbon atoms, e.g., ethylene oxide, propylene oxide and butylene oxide.The preparation of polymers from these compounds is described in Ellis,The Chemistry of Synthetic Resins (1935), pages 990 to 994. Thesecompounds are also referred to as polyalkylene glycols and their use assensitizers for silver halide emulsions is described in U.S. Patents2,423,549 and 2,441,389. The alkylene oxide derivatives may be preparedby condensing an organic compound containing an active hydrogen atomwith an alkylene oxide polymer, or by condensing the active hydrogencompound with the alkylene oxide during the polymerization of the lattermaterial.

Various derivatives of alkylene oxides may also be used to sensitize theemulsions, e.g., condensation products of alkylene oxide with organiccompounds containing an active hydrogen atomf Examples of activehydrogen organic compounds, i.e., compounds in which a hydrogen atom maybe replaced by reaction of the compound with metallic sodium,methylmagnesium iodide, etc., include alcohols, amines, mercaptans,acids, amides, hydrocarbons, such as acetylene, and compounds having Thealkylene oxides the active hydrogen in a methylene group such asdibenzoylmethane. More specifically, We may employ condensation productsof alkylene oxide with glycols, such as those having from 8 to 18 carbonatoms as described in U.S. Patent 2,240,472 and British Patent 443,559as well as condensation products of alkylene oxides with aliphaticalcohols, condensation products of 2,400,532 may also be employed.

In each case the polyalkylene oxide or derivative of alkylene oxideshould have :a molecular Weight of at least 300. Condensation productsof ethylene oxide with long chain alcohols, acids, amines or amidesshould have a molecular weight of about 700. In general, the bestresults are obtained with the condensation products of ethylene oxidewith long chain compounds having a chain length of 12 or more carbonatoms and with ethylene oxide polymers having a molecular weight of 1500to 4000 or more.

The alkylene oxide derivatives used to sensitize the emulsions may beillustrated by .the following specific examples, although our inventionis in no way limited to the use of these specific compounds.

HOCH CH O(CH CI-I O) CH CH OH Polyethylene glycol 0 (OH2OH2O)]JCH2CHQOH(CHQm O(OH2OHZO),,CH1OH OH Di-(polyethylene-glycoxy)-decane V n i HOCl-ICH O(CH CH O),,CH CH OC ';H V

Polyethylene glycol oleyl ether HOCH CH O (CH CH O) CH CH O-'CO--C -;H

Polyethylene glycol oleic ester where n=an integer greater than about10.

Polyethylene glycol nonyl phenol ether N-methyl myristylaminopolyethylene oxide N-methy1-n-dodecylamino polyethylene oxide Theanti-soumming effect of the S-thioctic acid was observed by preparing ahigh-speed gelatino-bromiodide emulsion containing the usual addenda,such as hardener, cyanine dyes, and stabilizers. The emulsion was thendivided into several batches and treated with the addenda indicated inTable II. The coatings are identified as a-d in the table. Separatesections of the coatings were exposed in an Eastman Type Ib sensitometeras indicated above with respect to Tables I and la, and the sectionsdeveloped in a normal developer (DK-SO') and another section in ahigh-solvent developer (BK-20). The speed, gamma and fog measurementswere measured in exactly the same fashion described above. DeveloperDK-50 has the same composition as the developer used in arriving at thedata in Table Ia, while Developer DK-20 has the following composition:

Water to make 1 liter.

In coating d of the following table, the S-thioctic acid was added to agelatin layer which was coated over the emulsion layer containing theoleyl ether of polyethylene glycol indicated in the table. The amountused in the separate coating d equalled the coverage in part c.Development for the coatings with DK-SO was for minutes, whiledevelopment time was 17 minutes for DK-20. The results obtained were asfollows:

velopers are used with emulsions sensitized with polyethylene glycols.Polyvinyl pyrrolidone may be incorpo rated in such emulsions in amountsup to about grams per mole of silver or in a gelatin overcoating for theemul.

sion in amounts of from 1 gram to 15 grams per mole, of silver in theunderlying emulsion. Polyvinyl pyrrolidone may be used in the developingsolution in amounts of from about 0.05 gram to 0.5 gram per liter ofdeveloper.

Table II Emulsion Addenda Developer DK-50 Developer DK- (g. mol. AgX)Coating Number Oleyl 5-Thioetic Speed Gamma Fog Speed Gamma Fog ScumEther Acid None None 325 95 .05 313 1. 12 17 None.

0.75 None 338 92 06 311 89 .20 Heavy. 0.75 0. 75 334 90 .04 289 1.05 13Very Slight. 0. 75 None 335 93 05 292 1.03 .15 Do.

In exactly the manner described above with respect to the data of TableII, a number of alkylene oxide polymers were used to sensitize separateportions of the same high-speed negative bromiodide emulsion. Thesecoatings were developed for 17 minutes in DK-ZO developer after exposurein the usual manner in a continuous step wedge. In the following table,sensitizer 1 is the oleyl ether of polyethylene glycol having amolecular weight of about 1500, sensitizer 2 is polyethylene glycolhaving a molecular weight of about 1540, sensitizer 3 is polyethyleneglycol-bis-carboglutamic acid sodium salt, and sensitizer 4 is3,6,9,12,l5,18,2l,24-octaoxahexacosane-bispyridinium perchlorate. Thespeed, gamma and fog for At the lower concentrations the polyvinylpyrrolidone not only lowers fog but changes the image tone from brown toblack.

What we claim as our invention and desire secured by Letters Patent ofthe United States is: l. A photographic silver halide emulsioncontaining (a) an alkylene oxide polymer selected from the groupconsisting of polyalkylene glycols and condensation products of alkyleneoxide containing from 2 to 4 carbon atoms with an organic compoundcontaining an active hydrogen atom selected from the class consisting ofalc0-' hols, phenols, amines, mercaptans, acids, amides, andhydrocarbons, said alkylene oxide polymer having a molecthe coatings areindicated in the table, these data being 5 ular weight of at least 300,and (b) S-thioctic acid.

obtained in the same fashion described above.

2. A photographic silver halide emulsion containing Table III SensitizerNo 5-Thioctic Acid 5-Thioctic Acid (.75 g./mol. AgX) Coating (gm/moi.Number AgX) Speed Gamma Fog Scum Speed Gamma Fog Scum 280 .82 10 None272 91 10 None. 270 66 12 Heavy 265 .86 10 Little. 283 .79 11 Little-.-273 90 10 Very Little. 281 .83 .12 do 270 .89 .10 None. 279 90 14 do 26788 .13 Do.

Alkylene oxide polymers containing anionic and cationic groups can alsobe used in our invention, including quaternary ammonium, quaternarysulfonium and quaternary phosphoniurn derivatives. Sensitizer 3 in TableIII is an example of an anionic alkylene oxide derivative. Sensitizer 4in Table III is an example of a quaternary ammonium alkylene oxidepolymer derivative. Other examples of anionic and cationic derivativesof alkylene oxide polymers which can be employed in our invention can beprepared as described in Carroll, Sagal and Beavers US. application Ser.No. 627,135, filed December 10, 1956. Such derivatives generally have amolecular weight of about 200 to 1500. Other examples of such polymersand their derivatives are shown in Carroll, Graham, Elins and Wilson US.application Serial No. 627,136, filed December 10, 1956.

It has also been found that fog may be reduced and that scum on thesurface of the film may be suppressed, by incorporating polyvinylpyrrolidone in an emulsion which has been sensitized with polyethyleneglycols as described above. Similar reduction of fog and suppression ofscum may be accomplished in emulsions so sensitized by incorporating thepolyvinyl pyrrolidone in a protective gelatin overcoat on the emulsion,or in the developer in which the emulsion is developed.

Scum on the surface of the film is particularly promoted by developerscontaining the thiocyanate ion such as Kodak Developer DK 20, especiallywhen such de- (a) an ethylene oxide polymer selected from the groupconsisting of polyethylene glycols and condensation products of ethyleneoxide with organic compounds containing an active hydrogen atom selectedfrom the class consisting of alcohols, phenols, amines, mercaptans,acids, amides, and hydrocarbons, said ethylene oxide polymer having amolecular weight of at least 300, and (b) 5- thioctic acid.

3. A photographic silver halide emulsion according to claim 2 whereinthe silver halide is silver bromiodide.

4. A photographic gelatino-silver-halide developing-out emulsioncontaining (a) a condensation product of ethylene oxide and a monohydricaliphatic alcohol containing at least 12 carbon atoms, said condensationproduct having a molecular weight of at least 1500 and (b) 5 thiocticacid.

5. A photographic gelatino-silver-halide developing-out emulsioncontaining (a) a condensation product of ethylene oxide with an organiccompound containing an active hydrogen atom selected from the groupconsisting of alcohols, phenols, amines, mercaptans, acids, amides, andhydrocarbons, said condensation product having a molecular weight of atleast 300, and (b) S-thioctic acid.

6. A photographic silver halide emulsion containing (a) the oleyl etherof polyethylene glycol having a molecular weight of at least 700 and (b)5-thioctic acid.

7. A photographic silver halide developing-out emulsion containing (a) apolyethylene glycol having a.

9 molecular Weight of at least 300 and (b) S-thioctic acid.

8. A photographic silver halide emulsion containing (a) polyethyleneglycol-bis-carboglutamic acid alkali metal salt having a molecularWeight of at least 300 and (b) S-thioctic acid.

9. A photographic silver halide developing-out emulsion containing (a)3,6,9,12,15,18,21,24-octaoxahexacosane-bis-pyridinium perchlorate and(b) S-thioctic acid.

10. A photographic silver halide emulsion stabilized by the addition ofat least 0.25 g. per mole of silver halide of S-thioctic acid.

11. A photographic silver bromiodide emulsion stabilized by the additionof at least 0.25 g. per mole of silver bromiodide of S-thioctic acid.

12. A method of preventing scum during the development of an exposedphotographic silver halide emulsion containing a sensitizer selectedfrom the group consisting of polyalkylene glycols and condensationproducts of an alkylene oxide containing from 2 to 4 carbon atoms withan organic compound containing an active hydrogen atom selected from theclass consisting of alcohols, phenols, amines, mercaptans, acids,amides, and hydrocarbons, said alkylene oxide polymer having a molecularweight of at least 300, comprising developing said ex- 10 posedphotographic silver halide emulsion in the presence of S-thioctic acid.

13. A photographic element comprising a support and coated on saidsupport at least 2 gelatin layers, at least one of said gelatin layerscontaining light-sensitive silver halide, sensitized with an alkyleneoxide polymer selected from the group consisting of polyalkylene glycolsand condensation products of an alkylene oxide containing from 2 to 4carbon atoms with an organic compound containing a reactive hydrogenatom selected from the class consisting of alcohols, phenols, amines,mercaptans, acids, amides, and hydrocarbons, said alkylene oxide polymerhaving a molecular Weight of at least 300, and at least one of saidgelatin layers containing S-thioctic acid.

References Cited in the file of this patent UNITED STATES PATENTS JonesMay 10, 1955 Mochel Dec. 27, 1955 OTHER REFERENCES Bullock et al.: J.Am. Chem. Soc., 74, 3455 (1952).

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING (A) AN ALKYLENEOXIDE POLYMER SELECTED FROM THE GROUP CONSISTING OF POLYALKYLENE GLYCOLSAND CONDENSATION PRODUCTS OF ALKYENE OXIDE CONTAINING FROM 2 TO 4 CARBONATOMS WITH AN ORGANIC COMPOUND CONTAINING AN ACTIVE HYDROGEN ATOMSELECTED FROM THE CLASS CONSISTING OF ALCOHOLS, PHENOLS, AMINES,MERCAPTANS, ACIDS, AMIDES, AND HYDROCARBONS, SAID ALKYLENE OXIDE POLYMERHAVING A MOLECULAR WEIGHT OF AT LEAST 300, AND (B) 5-THIOCTIC ACID.